9.13.
5 Applications of NMR
Structure Determination
The elucidation of molecular structure
using NMR spectra Is essentially the determination of the
chemical shitt and spin-spin coupling constant When the spectrum is recorded under low resolution
the intensities of the ines tell us about the ratio of
the same atoms in different chemical environments
The chemical shift of the
signal gives idea about the functionai groups present in the molecule
us
The spin-spin coupling constants allow us to determine the
arrangement of the atoms
Intermolecular Exchange Reactions
If a nucleus undergoes exchange between two
chemically different sites, the width of the resonance
ine depends on the rate of exchange From a study of the
broadening of spectral l1nes, it is possible
to evaluate the rate constant for the
exchange reaction
Hydrogen Bonding Studies
The chemical shift of the signal of a hydrogen bonded proton is more than that of a normai proton
From a measurement of the shitft, we can estimate the strength of the hydrogen bond
NMR Imaging
Nuclear Magnetic Resonance Imaging (NMR) is a new diagnostic technique that has revolutionized
medical imaging and biomedical research. In this process of imaging, the resonance of tissues over
a region of interest is obtained to understand its pathological state. This is achieved by using
variable magnetic fields. Eighty percent of the atoms in human body are hydrogen atoms and
therefore MRI can effectively be applied. Some of the advantages of using MRI are u) ts supersor
contrast resolution, (i) permits imaging of entire three-dimensional volumes simultaneously.
in) total absence of harmful radiations like X-rays, Y-rays, etc. and (iv) poss1b1lity of scan in any
predetermined orientation
9.14.4 Applications of ESR Spectroscopy
The presence of an unpaired electron is a must for the observation of ESR
spectrum. Hence, the
applications of ESR as an analytical tool limited. Stull the technique is used for
is
investigating
number of phenomena in paramagnetic systems. We briefly discuss some of them in this section.
Nuclear Spin and Hypertine Splitting
An ESR line splits into (2i + 1) hyperfine components and the amount of splitting depends on the
hyperfine coupling constants. Therefore, a study of the ESR spectrum of a sample gives the nuclear
constant of the nucleus to which the free electron is attached. It
spin and the hyperfine coupling
may be noted here that the
nuclear spin of Cr, Er, and "Pa were determined by this method.
determined by other methods were checked. Hyperfine
In many other cases, he nuclear spin
on the nucleus.
constant throws light on he electron density distribution
COupling
Structure of Free Radicals
electrons.
the structure of the free radicals.
Often ESR IS used to determine
Free radicals contain free determination of the structure of the free
radical CH3. Its
of this kind is the
An interesting example radicals CH and
and tetrahedral. From the ESR spectra of the free
possible structures are planar radical is which corresponds to sp
planar
hybridizat1on
the structure of the
CH, it is found that
of the carbon atom.
kinetic properties of biomolecules can
and
Certain nportant information regarding the chemical portion of the biomolecule and its
be obtained using ESR. A particular radical is attached to a
Then the same radical or a different
Cnvironnment is studied with thehelp of the ESR of the radical.
is attached to another portion of the biomolecule and the
environment in that region is studied.
drcal biomolecule is obtained.
This process is continued and idea about the different regions of the
Study of Symmetry in Crystals
From ESR studies of ions in of the crystal field in a crystal and hence the
crystal, the nature
symmetry can be established.
Spectroscopic Splitting Factor
If 8o is the g-factor of a standard sample and 8i is the g-factor of an unknown sample,
80 B
Bo
81
where Bo and B, are the fields required for resonance in the two cases. Substituting the values of
8o, Bo, and B1, the value of gi can be calculated.
Mössbauer Spectroscopy 13
Mössbauer spectroSCopy, a complementary tool to other established spectroscopic teci
nigues such as NMR, ESR and NQR, mainly deals with the nuclear resonant absorption and
fluorescence. Though this type of resonant absorption of rays was suggested by Kuhn in
1929. it was observed only in 1958 by Mössbauer because of the high recoil energy of the
nucleus whhich emitted the high energy Yrays. Mössbauer spectroscoP! is the study of the
ray absorption (or emission) spectra for transitions between nuclear states. It has now
hecome a very powerful tool for understanding problems in different branches of science.
19bl- Nob paize
13.1 RECOILLESS EMISSION AND ABSORPTION
Nuclear resonance absorption is in principle expected to occur when gamma radiation
kind
emitted in a transition from E; to E, is reabsorbed by another nucleus of the same
not be achieved due
according to the scheme depicted in Figure 13. 1. However, this could situation in detail.
to the high energy of the emitted photon. Let us now examine the
-E, -E,
absorption
emission
absorption.
Figure 13.1 uclear resonance
ground
a nuclear excited state E; above the
Lonsider an isolated atom of mass M having the recoil
E, be the energy difference E, - E, and Ere be the kinetic energy of
Slate E,. Let
hucleus. If p is the recoil momentum
(13.1)
E,. = 2M
have an energy
As this energy has to come from Eo, the emited gamma-ray will
(13.2)
E, = E, - Ere
351
352 Molecular Structure and Spectroscopy
Therefore, the centre of the emitted spectral line will be shifted from the expected position
E, (Figure 13.2). By the law of conservation of momentum,
Recoil momentum of the atom = Momentum of the emitted Y-ray
p =
C
(13.3)
where c is the velocity of light. Hence,
Ere =
2M
E (Eo E,)' E
(13.4)
2 Me? 2 Me? 2 Mc'
since E, is small compared to Eo:
After absorption of the gamma ray by the same nucleus, the atom will have momentum
and energy. This energy has to come from the radiation. Hence, in the absorption process,
to excite the nucleus upto the same energy the gamma ray must have the energy E, given
by
E, = Eo + Ere (13.5)
The effect of recoil is thus to introduce a difference of (E, - E,) between the energies of
the emitted and absorbed gamma rays in a resonant procesS
E
E, - E, = 2 Ere = Me (13.6)
If 2E,, <«|, the FWHM of the line, the two curves would overlap and one would observe
resonant absorption. Since E,. is proportional to Eo, it increases appreciably as we go
from the optical region (~2 eV) to the gamma ray region (-10 keV) of the electromagnetic
spectrum. Figure 13.2 illustrates the overlapping of emission and absorption lines, greater
the overlap greater is the absorption. Thus, maximum absorption will occur when the recoil
energy is zero. This can be achieved when the emitting and absorbing nuclei are bound in
crystal lattices. In such a case, the recoil energyis absorbed by the crystal lattice as a
whole. This is what Mössbauer did to observe the resonance
by placing a suitable unstable nucleus in a matrix which absorption] In other words,
absorbs most of the recoil energy
one gets a good Mössbauer source. When this gamma ray is passed
through a material
containing a similar nucleus, absorption will occur.
Emission Absorption
Eo- Ere E E, + Ere
Figure 13.2 Overlap of emission and absorption lines in a
nuclear transition.
Mössbauer Spectroscopy 353
13.2 EXPERIMENTAL TECHNIQUES
To design an eXperiment to investigate Mössbauer effect. as already mentioned, so
matrix containing the excited nuclei of a gjven isotope called the source is placed he
asecond matrix containing the same isotope in the ground state called the absorber. we ae
also seen that the amount of overlap of the energy profiles for the source and absorber
decides he strength of resonant absorption. A movement of the source and absorber relauve
lo each other with velocity u' produces a Doppler shift in frequency equal to (vlc) v, where
cis the velocity of light and v is the frequency of the ray. If the effective resonance
energies TOr source and absorber exactly match at a particular velocity v, the resonance
absorption will be at a maximum. Thus, the principle of obtaining Mössbauer spectrum is
to record the transmission of y-rays from a source through an absorber as a function or
the Doppler velocity v between the source and absorber.
13.2.1 Source and Absorber
with which the Mössbauer effect
The absorbers are normally stable isotopes of elements
can be observed. As emitter (source), one selects the excited
state of the very same isotope.
on the lifetime of excited state, nuclei
As the natural width of the resonance line depends
10<t< 10- s are usually selected as the source.
with excited state lifetimne in the range
linewidth too broad to be useful for hypertine
Short lifetime (< 10 s) would make the
too narrow resonance line which makes
studies. Longer lifetime (> 10° s) leads to to 'Fe
probable. Consider the source 'Co (| = 7/2, eQ< 0) which decaysemission
overlapping less nucleus comes to the stable 'Fe
through
capture. This excited
through electron
energy diagram is shown in Figure 13.3. For studies, sources of
of rays. The complete electrodeposition and subsequent diffusion in thin
metallic foils.
"Co have been prepared by Cr and Pd, etc. Iron foil is not suitable as it
induces
steel, Cu,
such as 310 stainless Mösshauer transition in
hyperfine splitting. Anothercommonly used source is the 23.9 keV also
form of Pd,Sn or BaSnO. The decay scheme of 1mgn is
"Sn, which is made in the
gIven in Figure 13.3.
(Tn=270 days)
SCo I= 7/2
119mn 11/2 89.5keV
Electron (T =245 days)
capture
136.4 keV
S/2 (8.6x 10s)
23.9 keV
(10%) (90%) 119gn' 3/2
(1.9 x 10 s)
14.4 keV
3/2
(10 s)
19Sn 1/2
SFe 1/2 0
(b)
(a)
showing the energy levels in Fe, (b) 1mSn,
Figure 13.3 Decay scheme of (a) "Co
showing the energy levels in 19Sn.
356 Molecular Structure and Spectroscopy
sec
Counts
per
Relative velocity
Figure 13.6 Typical Mössbauer spectrum.
13.3 ISOMER SHIFT
In a Mössbauer experiment, if the environments of the emitting and absorbing nuclei are
different, the energy of the nuclear transition Eo may differ by a small amount. This energy
difference is known as the isomer shift (8) or chemical shift. The efect of isomer shift
on the Mössbauer spectrum is to shift the resonance line from the zero position. The value
of can be positive or negative depending on the sample (Figure 13.7). Isomer shift is the
term more widely used since this effect depends on the energy difference in the ground and
excited (isomeric) states.
cm/s mm/s
S=-0.05 8= 1.21
(a) (b)
Figure 13.7 Isomer shift in (a) [Fe(CN)EJ", (b) (C,H;),Sn.
Isomer shift arises because the nucleus of an atomn is not a point
but has a finite charge distribution. The electrostatic interaction betweencharge
as assumed,
the nuclear charge
distribution and the electron charge distribution brings about a change in the energy levels
of the nucleus. The shift in the energy levels of the nucleus is given by
AE = (13.7)
Mössbauer Spectroscopy 357
where TV(ON" represents the total electron density at the site of the nucleus. ve a
interested in the change in energy SAE) between the nuclear ground and first excited State
(Figure 13.8). Hence,
(13.8)
S(AE) = (AE)e, - (AE)gr = e Iwo) (R - R)
Writing R for radius of the equivalent sphere of uniform charge distribution and ax
for (Rex - Rg)
(Rex - R:) = 2R dR = 2R2 ak
R